Vermiculite test



United States Patent 3,268,401 TRIARYLBORANE COMPLEX COMPOSITION AND METHOD FOR SEED PROTECTION Herman A. Birnbaum, Mendota Heights, and Harvey L. Anderson, Dellwood, Minn., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware No Drawing. Filed June 15, 1964, Ser. No. 375,318 16 Claims. (Cl. 167-38) This is a continuation-in-part of the copending application Serial No. 186,874 filed on April 12, 1962.

This invention relates to the protection of seeds from soil-borne organisms. In one aspect, the invention relates to a process for the protection of seeds from soil-borne organisms. In another aspect, the invention relates to compositions for the treatment of seeds to protect them from soil-borne microorganisms.

Soil-borne organisms which cause decay of crop seeds, damping off of young plants, etc. are responsible for large scale agricultural losses. To prevent or reduce these losses, seeds are frequently treated with various chemicals which are toxic to the organisms. Often, however, levels of treatment sufiicient to protect the seeds from the organisms also adversely affect the seeds themselves (i.e. exhibit phytotoxicity). In many cases, a degree of phytotoxicity is tolerated in seed treatments in order to obtain the desired protection against the soil-borne organisms.

Among the most effective seed treating agents are certain triarylborane complexes (see U.S. Patent 3,062,708). It has been found however that these complexes by themselves or mixed with inert diluents, such as diatomaceous earth, clays, etc. are somewhat phytotoxic. It is therefore much to be desired to reduce the phytotoxicity of these complexes without adversely affecting their elfectiveness against the soil-borne organisms.

It is therefore an object of this invention to provide a novel process for the protection of seeds.

It is another object of the invention to provide a new and valuable class of seed protectant compositions.

It is another object of the invention to provide seed protectant compositions with little or no phytotoxicity.

It is a further object of the present invention to provide a process for the protection of seeds from soil-borne microorganisms.

It is a still further object of the invention to provide seeds coated with a composition which greatly reduces the effect of soil-borne microorganisms on them.

Other objects will become evident from the disclosure which follows.

In accordance with the above and other objects of the invention, it has been found that seeds of crop plants (such as pea, corn, bean, oat, barley, cucumber, radish, flax, tomato, etc. seeds) can be effectively protected against soil-borne microorganisms and other destructive biological agents present in soils by the application thereto of a relatively small amount of a composition comprising a complex of a triarylborane with a Lewis base having a pK less than about in admixture with a finely divided solid compound which buffers to a pH above about 6 in its saturated solution. As used herein the buffer includes not only compounds which resist any change in pH upon addition of acid or alkali but also those which resist a decrease of the pH to below about 6 but do not resist increases in pH. The preferred buffers of the invention buffer to a pH of from about 7.5 to 12.5.

The triarylborane complexes and the buffering agents according to the invention have been found to be highly synergistic with respect to seed protectant activity. The buffering agent alone has no effective activity as a seed protectant while the triarylborane complexes alone are considerably less active against the damping off and seed decay organisms of the soil and have greater negative effects on the seeds themselves than do the compositions of the invention. While the reasons for this synergistic action are not fully understood, it may be that the seed safety is improved by decreasing the actual contact between seed and the complex and the effectiveness of the compositions against the soil-borne microorganisms is due to the chemical stabilization of the active triarylborane complexes by buffering them to a pH range in which they do not readily degrade. Regardless of the mechanism, which has no effect on the invention per se, the compositions of the invention have been found to be highly useful seed protect-ants.

The compositions of the invention are generally applied to the seeds at a rate of from about 0.03 to 1.0 ounce of the triarylborane complex and from about 0.09 to 10 ounces of the buffering agent per pounds of seed although greater or lesser rates of application will occasionally be desirable, depending upon the particular seeds and field conditions encountered. Ordinarily, but not necessarily, the weight ratio of the triarylborane complex to the buffering agent Will be from about 1:3 to 1:10.

The compositions according to the invention are preferably applied to the seeds in solid (dust) formulations although slurry or liquid formulations can be used. The solid formulations can consist entirely of the triarylborane complex-buffering agent composition or additives, such as extending agents, solid wetting agents, stickers, and the like can be added. Thus, hydrated silica, diatomaceous earth, etc. are suitable extending agents. Mixtures of triarylborane complexes and/ or mixtures of the buffering agents can also be utilized in particular seed treatment compositions of the invention when desired. Aerosol OT-B, primary dioctyl sodium sulfosuccinate; Renex 35, polyoxyethylene tridecyl alcohol plus urea; Triton X-100 isooctylphenyl polyethoxyethanol; Alkanol B sodium alkyl naphthalene sulfonate and fatty alcohol sulfates; etc. are suitable solid wetting agents. Low volatility solvents such as glycols, heavy mineral, vegetable or fish oils are suitable stickers; etc. The solid (dust) compositions of the invention can be applied directly by tumbling them with weighed amounts of seed until the latter is uniformly and evenly coated with the desired amount of chemical.

To prepare slurry or liquid seed treatment compositions, the triarylborane complex and the buffering agent can be dissolved, along with a suitable surface active agent and possibly other additives if desired, in a solvent, such as water, dimethylformamide, N-methyl pyrrolidone, acetone, methanol, tetrachloroethylene, methyl chloroform, methylene chloride, chloroform, mineral oil and the like. The slurry or liquid seed treatment composition can then be applied to the seeds using known techniques, e.g. with a conventional slurry treater or by spraying or tumbling onto the seeds.

Broadly speaking, the process for the preparation of the triarylborane complexes comprises preparing an ether solution of the triarylborane and introducing the desired Lewis base. The complexes appear to form in mol-formol proportions, and ordinarily, there is immediate precipitation of the ether-insoluble complex. The operation is carried out in the absence of air. Specific directions for the preparation of the complexes of triphenylborane are set forth in Berichte, vol. 57B, p. 813 if, 1924, while other triarylboranes and their complexes are described in the same Journal, vol. 61B, p. 271, 1928; vol. 6313, p. 934 if, 1930', and vol. 6413, p. 2112, 1931; and in An nalen, vol. 573, p. 195, 1951.

The triarylborane portions of the complexes are exemplified by triphenylborane, alkyl-substituted triphenylboranes such as tri-p-tolyl borane and tri-p-xylyl borane, halogen-substituted triphenylboranes such as tri-(p-fluorophenyl) borane, alkoxy-substituted triphenylboranes such as triphenetyl borane (i.e. tri-p-ethoxyphenyl borane) and tri-(p-methoxyphenyl) borane, trinaphthyl borane, arylsubstituted triphenylboranes such as tri(p-biphenyl) borane, aryloxy-substituted triphenylboranes such as tri(4- phenoxyphenyl) borane, arylthio-substituted triphenylboranes such as tri(4-phenylthiophen l) borane and the like. Triphenylborane is preferred in the formation of the complexes used in the invention because it is readily prepared from chlorobenzene and bromobenzene, which are readily accessible, and is highly effective in the process of the invention. A convenient method for the preparation of triphenylborane is the reaction of a metallic derivative of bromobenzene such as phenyl magnesium bromide with boron trifiuoride, as described in Berichte, vol. 55B, page 1261 (1922).

The term pK is used herein in its conventional meaning, i.e. the negative logarithm of the ionization constant K Lewis base complexing agents suitable for use in the preparation of the complexes are, for example, ammonia (pK 4.74), methylamine (pK 3.19), dodecylamine (pK 3.7), n-tetradecyl amine (pK 3.8), ethylenediamine (pK, 4.07), hexamethylene diamine (pK ca. 4), tetrahydrofurfuryl aminoethanol (pK ca. 5), acetylacetone imide (pK ca. 5), benzy-lamine K; 4.62), triethylenetetramine (pK ca. 3), N-alkyl propylene diamines such as 12-(N- dodecyl propylamine) (pK; ca. 3), dimethylamine (pK 3.31), di-n-propylamine (pK 3.0), N-methylethanol amine (pK ca. 5), piperidine (pK 2.79), piperazine (pKi, 4.19), morpholine (pK- ca. 5), trimcthylamine (pK 4.13), tri-n-propylamine (pK 3.26), 3-dimethylaminopropylamine (pK; ca. 4), tributylphosphine (pK ca. 3), phenyldiethy lphosphine (pK ca. 4), phenyldipropylphosphine (pK 3.4), pyridine (pK, 8.64), 3-bromopyridine (pK 7.82), 'y-ethylpyridine (p-K ca. 8.6), 3-(4- pyridyl)-propanol-1 (pK 8.6), 3,5-dichloro-pyridine (pK ca. 9) bis(4-pyridyl)glycol (pK ca. 8.6), nicotine (pK- 6.05), isonicotinic acid (pK 021.10), n-butyl nicotinate (p-K ca. 8.7), nicotinamide (pK 8.64), isonicotinic thionamide (pK ca. 9), fi-picoline (pK 7.96), 'ypicoline (pK 7.96), imidazole (pK 4.37), metallic bases including alkali and alkaline earth metal hydroxides, such as sodium hydroxide (pK 1), potassium hydroxide (pK 1), and the like.

The following descriptions, including uncorrected melting points where available, of a number of the complexes will serve to characterize them and are generally illustrative of the complexes useful in the invention.

M.P. or appearance Triphenylborane-ammonia '179183 C. Triphenylborane-methyl amine 195-213 C. Triphenylborane-dodecyl amine Tan grease. Triphenylborane-n-tetradecyl amine Tan oil. Triphenylborane-triethylenetetramine 75-84" C. Triphenylborane-duomeen S 1 Red,l viscous o1 Triphenylborane-duomeen 12 1 Do. Triphenylborane-duomeen C 1 Do. Triphenylborane-dimethylamine 157166 C. Triphenylborane-piperidine Ivory wax. Triphenylborane-piperazine l70175 C.

Triphenylborane-trimethylamine 132-138 C.

Triphenylborane-pyridine 182-202 C. Triphenylborane-3,S-dichloro-pyridine 1l2'l15 C. Triphenylborane-bis(4-pyridyl) glycol 173181 C. Triphenylborane-v-picoline -145 C. Tn'phenylborane-imidazole 185-190" C. Triphenylborane-sodium hydroxide White solid,

does not melt below 300 C. Tri(a-naphthyl)borane-ammonia 153157 C. Tri(a-naphthyl)borane-diethylamine -175 C. Tri(u-naphthyl)borane-trimethylamine 156l58 C. Tri(p-fiuorophenyl)borane-arnmonia 179 181 C.

T ri(p-fluorophenyl)borane-triethylamine 110-115 C. Tri(p-methoxyphenyl)borane-ammonia 138-142 C. Tri(p-tolyl)borane-ammonia 143-156" C.

The Duomeens are products of Armour and Company of Chicago, Illinois. Chemically they are N-alkyl trimethylene diamines. The alkyl group in Duomeen S is derived from soya. fatty acid, in Duomeen 12 is derived from Cm fatty acid and in Duomeen C is derived from coconut fatty acid.

'Among the buffering agents useful for purposes of the invention are the following: barium acetate, barium hydroxide, calcium acetate, calcium hydroxide, calcium sulfate, lithium carbonate, lithium hydroxide, magnesium acetate, magnesium carbonate, magnesium phosphate, magnesium sulfate, nickel acetate, potassium acetate, potassium bicarbonate, potassium carbonate, potassium phosphate, potassium sulfate, sodium acetate, sodium bicarbonate, sodium carbonate, sodium phosphate, strontium acetate, strontium sulfate, zinc acetate, etc.

The following examples illustrate methods and compositions used in practicing this invention, but are not to be construed as limiting the scope thereof in respect of the compositions or complexes to be employed, or the organisms to be subjected to the compositions of the invention. The seed treatments of the invention are evaluated in the examples using Pythium soil and vermiculite greenhouse tests and in field tests. The details of the application of the treatments and of the tests are as follows:

APPLICATION OF THE SEED PROTECTANT COMPOSITIONS Weighed amounts of the finely divided components of the seed protectants and of the seeds are tumbled together until the seeds are uniformly and evenly coated. In cases Where the triarylborane complexes are liquids, they are mixed with and adsorbed by the solid components of the seed treatment before the seeds are added.

PYTHIUM SOIL TEST This test primarily measures the control of the Pythium organism by the seed treatment. Pythium is responsible annually for important economic losses and its control per se is of great value. This test, in which the treated seeds are subjected to soil which is heavily infested with the microorganism, however, serves as a dependable general screen for the evaluation of the general effectiveness of seed protectant compositions against soil borne microorganisms and other destructive biological agents present in soils (e.g. Rhizoctonia, Pythium, Anthracnose, etc.).

The treated seeds are planted in four-inch plastic pots containing soil heavily infested with Pythium. The pots are held in a refrigerator at 45 F. to 50 F. for a period of four days and are held for the remainder of the tests at approximately 75 F. The moisture level is maintained at about 25 percent of the water holding capacity of the soil. The lower temperature provides optimum conditions for the growth of the fungus organisms and relatively adverse conditions for the germination of the seeds while the higher temperature favors the seed germination. The results of this test are measured as percent emergence (the percentage of the seeds planted which send shoots up through the surface of the soil), average weight in grams per pot of plants resulting from seeds planted in Pythium soil (measured 17 days after planting) and height in inches of the plants (measured 17 days after planting). The average weight and height in inches are measured relative to the portions of the plants above the soil level. Control (3) Triphenylborane-ammonia complex alone (5% of essentially pure silicon dioxide added torender the chemical physically adaptable to a seed treatment preparation) (Lot F) lots of untreated seeds are generally included. 5 (4) Buffering agents alone (Lots G-I) 5) Inert diluents alone (Lots J-K) UI. TE TE VERMIC ST (6) No treatment (Lot L) This test measures the effects of seed treatments on In these tests seeds are planted per pot and 5 repthe seeds in the absence of the disease factor. Treated licates (pots) are used for each individual treatment. One and untreated seeds are planted in separate four-inch plas- 10 ounce of seed treatment per bushel of seeds is used in tic pots containing vermiculite of relatively small particle every case.

Additive Pythium Soil vermiculite Triphenylborane- Lot ammonia Percent Percent Average Percent Average complex Name by Emerplant Emerplant (percent by weight gence weight gence weight weight) per pot per pot Calcium hydroxide 75 95 .0 7 .2 96 .0 6 .3 25 Mangesium carbonate. 75 98 .7 7 .3 96 .0 5 .3

ICIMOHh 507 g 25 Ca Actate 10 75 96.0 8.6 94.6 6.7

Bentonite 5%. 25 Diatomaceous 75 92 .3 5 .6 90 .6 3 .1 25 Kaolin 75 93 .3 5 .3 90 .6 3 .2 95 Silicon dioxide- 5 90.7 4.8 92.0 3.7 0 Calcium hydroxide. 100 .8 0 .9 78 .6 5 .8 0 Magnesium carbonate. 100 16 .7 0.3 69 .3 6 .5

fia(OH)1 0570% g 0 Ca 100 38.7 0.8 85.3 6 1 Bentonite 5% 0 Diatomaceous eart 100 24.0 0 6 70.7 2 9 0 K21 1n 100 13 .7 0 2 92.0 6 1 33.3 0 6 89.3 4 4 size. The treatment and observation of the test pots are the same as in the Pythium soil test.

FIELD TEST Example 1 In this example the relative efiects of the following treatments on Laxtons Progress pea seeds are compared:

1) Triphenylborane-ammonia complex with buifering agents according to the invention (Lots A-C) (2) Triphenylborane-ammonia complex with inert diluents (Lots D-E) These test results indicate that the seed protectant compositions of the present invention (Lots A-C) are highly effective against the test organism (Pythium) and have no measurable phytotoxicity. The seed protestant compositions of the triphenylborane complex in admixture with an inert diluent and of the complex in essentially pure form (Lots D-F) exhibit significant phytotoxicity both in the percent emergence and in the average plant Weight in both Pythium and vermiculite tests and less effective activity against the test organism. The seed protectant compositions containing none of the triphenylborane cornplex exhibit little or no advantage over the untreated seeds.

Example 2 In this example the relative effects of various treatments on Laxtons Progress pea seeds are noted. The treatments include 1) various buffering agents alone, (2) the triphenylborane-amm'onia complex alone and (3) compositions according to the invention of triphenylborane-ammonia with various buffering agents.

Seed Treatment Composition Test Results Amount Triphenyl- Buffering agent of seed Percent Percent borane- Percent treatment emeremerammonla by weight (oz./bu.) gence gence complex (per- Name pH Pythium vermiccent by weight) soil ulite 0 1.0 73 41 0. 5 73 56 Potassium Sulfate 7 100 1. 0 0 100 Barium Acetate 67 100 1. 0 0 97 Magnesium Carbonate. 7 100 1. 0 0 95 Magnesium Sulfate -7 100 1.0 0 98 Calcium Hydroxide 12. 4 100 1. 0 0 95 Calcium Acetate. 6. 35 100 1. 0 O 98 Potassium Carbona 11. 6 100 1.0 0 93 Potassium Bicarbonat -8. 5 100 1. O 0 97 Potassium Phosphate 9 100 1.0 O 97 Potassium Bicarbonat -8. 5 87. 5 1. 0 83 0. 5 72 76 Potassium Phosphate 9 87. 5 1.0 97 73 0.5 68 Magnesium Carbonate 7 87. 5 1.0 83 98 0. 5 65 93 Calcium Hydroxide 12. 4 87. 5 1. 0 83 82 0. 5 72 85 25.0. do 12. 4 75.0 1. 0 85 72 0. 5 92 87 12.5 Calcium Acetate 6. 35 87. 5 1. 0 86 88 0.5 88 85 Example 3 I v In this example Pythium soil tests and vermiculite tests Buffering Agent Results are utilized to compare the growing characteristics of P P t ercent ercen Laxt ons Progress pea seeds treated with compositions of 5 Name PH Emergence Emergence the invention consisting of various buffering agents and A Pythium Verrniethe triphenylborane-ammonia complex with those of untreated pea seeds of the same type. The seed treatment compositions are 12 /2 percent triphenylborane-ammonia gggfig g? 2% complex, 75 percent buffering agent and 12 percent Magnesium Phosphate -7 79 88 finely divided silica, the latter being added as an aid in 10 gfigggg f g gggg :3 2% 3% compounding the mixture. The rate of seed treatment in itrgntiumj Sllfatet 7.2 2 1 mm ar 0H3 8 all cases is 0.5 ounce per bushel of seeds. Lithium Hydroxide 11 73 90 821 1 33 1% it 2% 0111111 (36 a e Buffermg Agent Test Results 15 Calcium Sulfate 6.25 65 35 Percent Percent Name pH Emergence Emergence Pythium Vermie- Soil ulite goutrol (Ugtregtedtseeds) 0 731 otassium at 0113. e 11.6 85 9 Potassium Bicarbonate -8. 5 79 90 Example 4 f,; 3 3 53 g; The following table presents data from tests run on Potassium Siniate -7 s1 90 Laxtons Progress pea seeds treated with a variety of com- 233113 *;f;;f.- 12 3? positions according to the invention, both the triarylgodium Acetate 9.0 73 90 borane complex and the bufit'ering agent being varied. 321% I Z II :3 33 The seed protect-ant compositions of this example all Barium Acetate 6-7 86 90 contain 25 percent of the triarylborane complex and percent of the bufiering agent.

Seed Treatment Composition Test Results Amount Triarylborane Complex Buffering Agent of seed Pythium Soil vermiculite treatment,

0z.,fbu. pK oi Percent Plant Percent Plant Name Lewis Name pH Emerg- Ht. in Emerg- Ht. in Base ence Inches ence Inches Control. none n 2 1 1.5 38 1.8

. 011.1111 3 0x1 e. .5 5 1. fiaB'Pyndme dn 74 1,5 93 0 Do 8. 64 Magnesium Sulfate -7 1 28 1. 0 93 1. 7 47 1.0 98 1.7 Do 8. 6. Magnesium Carbonate. 7 1 38 1. 2 95 1. 8 53 1.2 95 1.8 B-Dodecy1amine 3. 7 Calcium Hydroxide---" 12. 4 1 94 1. 5 90 1. 8 A 92 1. 5 93 1.5 Bis B-Piperazine 4.19 .do 12.4 1 95 1.4 95 1.9

y 68 1. 5 90 1.9 B'NaOH 1 Calcium Acetate 6. 35 1 31 0. 8 90 1. 6 B Methyl Ethanolamineca. 5 Calcium Hydroxide".-- 12. 4 1y 37 4 2 5 .5

Do ca. 5 Potassium Bicarbonate- -8. 5 1 83 1. 1 62 1.0 n 87 1.3 82 1.5 B-Piperidine 2. 79 Calcium Hydroxlde 12. 4 1 95 1. 5 98 1.8 A 97 1. 5 98 1.8 ;B-Diethylene Triamine ca. 3 d0 12.4 1 93 1.5 95 1.8 e A 95 1.5 90 1.7 Do ca. 3 Barium Acetate 6-7 1 87 1. 5 1. 5 1. 5 96 1. 7 Do ca. 3 Potassium Acetate 10 1 87 1. 2 93 1. 4 92 1.2 90 1.5 B-Trirnethylamine 4. 13 Calcium Hydroxide".-. 12. 4 1 90 1. 3 98 l. 6 85 1.3 as 1.8 Do 4. 13 Potassium Phosphate.-- 9 1 89 1.3 68 1, 2 89 1.3 96 1.5 3B-Amm0nia 4. 74 Calcium Hydroxide".-. 12. 4 l 92 1. 3 92 1. 6 89 1.3 93 1.3

Similar advantages over untreated seeds are obtained when treating compositions in accord with the invention containing tri(ot-naphthyl) boraneammonia, '[Ii(ocnaphthyl) borane-diethylamine, tri(a-naphthyl) boranetrimethylamine, tri(p-fluoropheny1) borane-ammonia, tri(p-fiuoropheny1) borane-triethylarnine, tri(p-methoxyphenyl) borane-ammonia, tri(p-tolyl) borane-ammonia,

19 tri(p-bipheny1) borane-ammonia, tri(4-phenylthiophenyl) borane-ammonia, tri(4-phenoxypheny1) borane-ammonia, etc., are used.

Example 5 A number of other compositions according to the invention are evaluated in this example on Laxtons Progress pea seeds.

Test Results Amount of seed Pythium Soil vermiculite Seed Treatment Composition (percent by weight) tz-eatligierit oz. u.

Percent Aver. Percent Aver. Emerg- Plant Emerg- Plant ence wt./pot 1 ence wt./pot 1 7 0.18 85 3. 28 Control, none 0 88 3. 31 0 0 92 3. 92 Calcium Hydroxide (75), Magnesium Carbonate (10),

Calcium Acetate (10), Bentonite 1 0 0 92 3. 54 Do 0 0 98 3.67 Do y. 0 0 92 2. 77

s Btrimethylamine (25), Calcium Hydroxide (75) 1 88 3.85 95 5.47 Do 95 4.68 92 4. 24 Do M 88 4. 08 87 3. 72 ;B-ammonia (25), Magnesium Carbonate 1 85 3. 31 98 4. 76 D 83 3. 42 95 4. 48 D0 M 70 2.46 92 3. 91 B-ammonia Calcium Hydroxide (65), Magnesium Carbonate (10), Calcium Acetate (10), Bentonite (5) 1 75 2. 77 97 4. 44 D0--- 85 3. 83 98 3. 67 D0 M 85 5. 53 92 3. 74

qSgB-ammonia Calcium Hydroxide (60), Magnesium Carbonate (10), Calcium Acetate (10), Bentonite (5) 1 85 3. 43 97 4. 60

0 92 4. 88 93 2.77 Do 92 5.00 97 3.57 oaB-ammom'a Calcium Hydroxide (55), Magnesium Carbonate (10), Calcium Acetate (10), Bentonite (5) 1 88 3. 22 95 3. 33 Do v 97 6. 52 98 3. 23 Do M 97 7.19 97 3.89

qSaBammonia Calcium Hydroxide Magnesium Carbonate (10), Calcium Acetate (10), Bentonite (5) 1 90 4. 48 98 3. 59 D0--. 92 5. 12 98 3.17 Do )4 100 5. 87 97 3. 31

1 There are three plants per pot. The value reported is the above the soil or vermiculite level) of all three plants.

Example 6 total weight in grams of the tops (i.e. the portion The following tests are on Golden Cross Bantam sweet corn seeds.

Seed Treatment Composition Test Results Amount Triphenyl- Buffering Agent of seed Percent Percent borane treatment emergemerg ammonia (oz./bu.) ence ence complex (percent Name pH Percent pythium vermicby weight) by weight soil ulite Control, none--- Control, none- 8 96 12.5 Barium acetate 6-7 87. 5 1 92 82 A 92 90 66 93 12.5 Potassium Carbonate 11.6 87. 5 1 83 72 $6 93 72 90 72 12.5 Magnesium Carbonate 7 87.5 1 82 95 92 92 $4 92 95 12.5 Magnesium Sulfate -7 87.5 1 83 80 A 82 93 M 68 93 12.5 Potassium Sulfate -7 87. 5 1 90 A 88 88 M 95 12.5 Calcium Acetate.-. 6.4 87.5 1 90 88 95 90 M 87 87 12.5 Potassium Phosphate 9 87.5 1 93 86 95 88 4 42 88 12.5 Potassium Bicarbonate -8. 5 87. 5 1 92 92 83 92 92 12.5 Calcium Hydroxide 12. 4 87. 5 1 93 92 A 95 82 M 95 73 25 do 12. 4 75 1 89 70 90 93 54 89 72 50 ..d0 12. 4 50 1 87 80 95 72 4 88 93 11 Example 7 The following are field tests which demonstrate the value of the compositions of the invention on various crops under normal conditions of use.

12 divided compound butters to a pH of from about 7.5 to 12.5.

13. A composition comprising a complex of a triarylborane selected from the class consisting of triphenyl- Dosage Test results Seed Seed treatment composition (oz.{100 lb. (percent of seed) emergence) Corn (Golden Cross Bantam sweet corn). None, control- 66. 8 o 25% @Bamrnonia, 75% calcium hydroxide l 77. 3 Cucumber (SMR-12) pickling cucumber) None, control-" 29. Do 25% NB-ammonia, 75% calcium hydroxide 2 50. 5 Do seB-ammonia, 2.156% calcium hydroxide, 37%% 6 56. 2

magnesium carbonate. Cotton (Machine delinted Stoneville No. 7) None, control--- 24. 0 Do 25% s Bammonia, 75% calcium hydroxide 1% 31. 7 D do 3 35.2 Do 25% B-ammonia, 37%% calcium hydroxide, 336% 3 36, 5

magnesium carbonate. Peas (Alderman) None, control"- 64. 6

Do 25% d3B ammonia, 75% calcium hydroxide None, control 31 25%d sgB ammonia, 75% calcium hydroxide 1 2 fl 25% B ammonia, 37%% calcium hydroxide, 37%% $6 40 magnesium carbonate. Sorghum (Midland) None, control 22 Do 25% a ti-ammonia, 75% calcium hydroxide 32 Do 25% (MB-ammonia, 3i'%% calcium hydroxide, 335% 31 magnesium carbonate.

What is claimed is:

1. The method of protecting seeds from soil dwelling organisms which comprises applying to said seeds before planting a composition comprising a complex of a triarylborane selected from the class consisting of triphenylborane, alkyl-substituted triphenylborane, halogen-substituted triphenylborane, alkoxy-su'bstituted triphenylborane, trinaphthyl bo-rane, tri-(p-biphenyl) borane, tri- (4-phenoxyphenyl) borane and tri-(4-phenylthiophenyl) borane with a Lewis base having a pK less than about 10 intimately intermixed with a finely divided solid compound which buifers to pH above about 6 in its saturated aqueous solution.

' 2. A method according to claim 1 wherein the Lewis 'base is pyridine.

3. A method according to claim 1 wherein the Lewis base is dodecylamine.

4. A method according to base is piperizine.

5. A method according toclaim 1 wherein the Lewis base is anethylethanolamine.

'6. A method according to claim 1 wherein the Lewis base is piperidine.

v7. A method according to claim 1 wherein the Lewis base is diethylenetriamine.

: 8. A method according to claim I wherein the Lewis base is trimethylamine.

9. A method according toclaim 1 wherein the finely divided solid compound is magnesium carbonate.

' 10. The method of protecting seeds from soil dwelling organisms which comprises applying to said seeds before planting a composition comprising a complex of triphenylborane with a Lewis base having a pK less than about 10 intimately intermixed with a finely divided solid compound which buffers to a pH above about 6 in its saturated 'aqueous solution.

claim 1 wherein the Lewis 11. The method according to claim 10 wherein said- Lewis base is ammonia.

12. A method according to claim 1 wherein the finely borane, alkyl-substituted triphenyl-borane, halogen-substituted triphenylborane, alkoxy-substituted triphenylborane, trinaphthyl borane, tri (p-biphenyl) borane, tri- (4 phenoxyphenyl) borane and tri-(4-phenylthiophenyl) borane with a Lewis base having a pK less than about 10 intimately intermixed with a finely divided solid compound which buffers to a .pH above about 6 in its saturated aqueous solution.

14. A composition comprising a complex of triphenylborane with a Lewis base having a pK less than about 10 intimately intermixed with a finely divided solid compound which bufiers to a pH above about 6 in its saturated aqueous solution.

15. A composition comprising a complex of a tria-rylborane selected from the class consisting of triphenyiborane, alkyl-substituted triphenylborane, halogen-substituted triphenylborane, alkoxy-substituted triphenylborane, trinaphthylborane, tri-(p-biphenyl) borane, tri- (4-phenoxyphenyl) borane and tri-(4-phenylthiophenyl) borane with ammonia intimately intermixed with a finely divided solid compound which buflers to a pH above about 6 in its saturated aqueous solution.

'16. A composition comprising a complex of a triarylborane selected from the class consisting of triphenylborane, alkyl-substituted triphenylborane, halogen-substituted 'triphenylborane, alkoxy-substituted triphenylborane, trinaphthyl'borane, tri-(p-biphenyl) borane, tri- (4-phenoxyphenyl) borane and tri-(4-phenylthi-ophenyl) borane with a Lewis base having a pK less than about 10 intimatel'y'iutermixed with finely divided solid calcium hydroxide.

References Cited by the Examiner j UNITED STATES PATENTS 3,062,708 11/1962 Updegrafl? l6730 3,140,977 7/1964 Duyfjes et a1 167-30 JULIAN LEVITT, Primary Examiner. GEORGE A. MENTIS. Assistant Examiner. 

